CN115058175A

CN115058175A - Coating compositions for use with overcoated photoresists

Info

Publication number: CN115058175A
Application number: CN202210808132.1A
Authority: CN
Inventors: M·格朗布瓦; M·Y·金; E·H·柳; J·H·沈; M·K·蒋; J-J·李
Original assignee: Rohm and Haas Electronic Materials Korea Ltd; Rohm and Haas Electronic Materials LLC
Current assignee: Rohm and Haas Electronic Materials Korea Ltd; Rohm and Haas Electronic Materials LLC
Priority date: 2015-08-31
Filing date: 2016-08-26
Publication date: 2022-09-16
Also published as: JP2017078846A; CN106479329A; KR102414899B1; JP6525376B2; KR20170028843A; TW201712062A; TWI659991B; KR20190057250A; US10788751B2; US20170059991A1; KR101982103B1

Abstract

A coating composition for use with an overcoated photoresist. The present invention provides a method of forming a photoresist relief image, comprising: a) coating a substrate with a layer of a coating composition comprising: 1) a resin comprising one or more cyanurate groups and a polyester bond; and 2) a crosslinking agent comprising the structure of formula (I); and b) coating a photoresist composition layer on the coating composition layer.

Description

Coating compositions for use with overcoated photoresists

The present patent application is a divisional application of the invention patent application having application number 201610742216.4, filed 2016, 26/8, entitled "coating composition for use with an overcoated photoresist".

Technical Field

The present invention relates to compositions, and in particular antireflective coating compositions, for microelectronic application compositions of the invention comprising a crosslinker of formula (I). The preferred compositions of the present invention are used with an overcoated photoresist composition and may be referred to as a bottom antireflective composition or "BARC".

Background

Photoresists are photosensitive films used for transfer of images to substrates. A photoresist coating is formed on a substrate and is subsequently exposed to an activating radiation source via a photomask. After exposure, the photoresist is developed, resulting in a relief image that allows selective processing of the substrate.

Reflection of activating radiation used to expose a photoresist typically places limits on the resolution of the image patterned in the photoresist layer. Reflection of radiation from the substrate/photoresist interface can produce spatial variations in radiation intensity in the photoresist, resulting in non-uniform photoresist linewidths upon development. Radiation can also scatter from the substrate/photoresist interface into regions of the photoresist where exposure is not intended, again resulting in line width variations.

One approach to reducing the problem of reflected radiation is to use a radiation absorbing layer interposed between the substrate surface and the photoresist coating. See U.S. published application 2007026458; 2010029556, respectively; and 2010009289; us patent 8334338; 8142988, respectively; 7691556, respectively; 7638262; and 7416821; and WO 2014185335.

For many high performance lithographic applications, specific antireflective compositions are utilized to provide desired performance characteristics, such as optimal absorption characteristics and coating features. See, for example, the patent literature referred to above. Nevertheless, electronic device manufacturers are continually seeking increased resolution of patterned photoresist images over antireflective coatings and in turn require ever increasing performance of antireflective compositions.

It would therefore be desirable to have a novel antireflective composition for use with an overcoated photoresist. It would be particularly desirable to have novel antireflective compositions that exhibit enhanced performance and can provide increased resolution of images patterned into an overcoated photoresist.

Disclosure of Invention

We now provide novel coating compositions that can be used with an overcoated photoresist composition. In a preferred aspect, the coating composition of the present invention can act as an effective antireflective layer for an overcoated resist layer.

In a preferred aspect, an organic coating composition, in particular an antireflective composition for use with an overcoated photoresist, is provided that includes a crosslinker component that is resistant to sublimation from a coating layer as may occur during thermal processing of the coating layer of the composition.

More specifically, coating compositions are provided that include 1) a resin; and 2) a crosslinking agent comprising the structure of formula (I) prior to reaction with the resin:

wherein in formula (I):

each R is independently selected from hydrogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted carbocyclic aryl, or optionally substituted heteroaryl,

wherein at least one R group is not hydrogen;

r' and R "are each independently selected from hydrogen, optionally substituted alkyl or optionally substituted heteroalkyl, optionally substituted carbocyclic aryl or optionally substituted heteroaryl.

In preferred aspects, at least two of the R groups are the same or different non-hydrogen groups, including where three or four of the R groups are the same or different non-hydrogen groups.

As referred to herein, "crosslinker before reaction with resin" means that prior to thermally induced hardening or other reaction of the crosslinker and resin components of the coating composition, such as during a photolithographic process in which a coating layer of the composition containing the resin and crosslinker of formula (I) will be heated for 30 seconds or more at more than 100 ℃.

In preferred aspects, the crosslinking agent of formula (I) above has a molecular weight of at least 300, 400, 500, 600, 700, 800, 900 or 1000 daltons. In certain aspects, the crosslinking agent has a molecular weight of less than 1500 daltons. In certain aspects, the crosslinking agent has a molecular weight between 400 or 500 daltons and 1500 daltons.

In other preferred aspects, the crosslinking agent of formula (I) is thermally stable or heat resistant, e.g., preferred crosslinking agents have a degradation temperature greater than 250 ℃. As referred to herein, the degradation temperature of the crosslinker material is defined as determined by the following protocol defined in example 11 below.

In a particularly preferred aspect, such thermally stable crosslinkers (e.g., having a degradation temperature greater than 250 ℃) also effectively function to crosslink the antireflective composition coating, i.e., the coating of a composition as disclosed herein comprising the crosslinker will harden to prevent undesirable intermixing with the subsequently applied fluid photoresist composition after heating the antireflective composition layer at 175 ℃ for 60 seconds.

For antireflective applications, the underlayer compositions of the present invention also preferably contain a component that contains a chromophore that can absorb undesirable radiation used to expose an overcoated resist layer from reflecting back into the resist layer. The resin or crosslinker may comprise such a chromophore, or the coating composition may comprise another component comprising a suitable chromophore.

In use with an overcoated photoresist, the coating composition can be applied to a substrate, such as a semiconductor wafer, which can have one or more organic or inorganic coatings thereon. The applied coating may optionally be heat treated prior to overcoating with the photoresist layer. Such heat treatment may cause hardening, including crosslinking, of the coating composition layer. Such crosslinking may include hardening and/or covalent bond forming reactions between one or more composition components and may adjust the water contact angle of the coating composition layer.

Thereafter, a photoresist composition can be applied over the coating composition layer, followed by imaging of the applied photoresist composition layer by patterned activating radiation and development of the imaged photoresist composition layer to yield a photoresist relief image.

A variety of photoresists can be used in combination (i.e., overcoated) with the coating compositions of the invention. Preferred photoresists for use with the underlying coating composition of the invention are chemically-amplified resists, especially negative-tone photoresists, which contain one or more photosensitive compounds and a resin component containing units that undergo deblocking or cleavage reactions in the presence of a photoacid.

In a preferred aspect, the photoresist composition is designed for a negative-tone resist, wherein the exposed regions remain after the development process, but positive-tone development can also be used to remove the exposed portions of the photoresist layer.

The invention further provides methods of forming photoresist relief images and novel articles comprising substrates (such as microelectronic wafer substrates) coated with the coating compositions of the invention, alone or in combination with a photoresist composition. Also provided are crosslinker materials of formula (I).

Other aspects of the invention are disclosed below.

Detailed Description

As discussed above, organic coating compositions, in particular antireflective compositions for use with an overcoated photoresist, are provided that include a crosslinker component that is resistant to sublimation from the coating as may occur during thermal processing of the coating of the composition.

Without being bound by any theory, it is believed that one or more components of the primer composition may migrate out of the applied coating during the photolithographic process. In particular, it is believed that during heat treatment of the applied coating composition to crosslink or otherwise harden the coating, one or more composition components may sublime or otherwise migrate from the coating. Such sublimation materials can compromise lithographic performance in a variety of ways, including by deposition on subsequently applied photoresist coatings.

As discussed above, we provide a coating composition comprising:

1) a resin; and

2) a crosslinking agent comprising a structure of formula (I) prior to reaction with the resin:

wherein in formula (I):

wherein at least one R is not hydrogen;

In the crosslinking agent of formula (I), preferred R groups include optionally substituted alkyl groups having from 1 to 20 carbon atoms, more typically from 1 to 12 or 15 carbon atoms; optionally substituted heteroalkyl having one or more N, O or S atoms and 1 to 20 carbon atoms, more typically 1 to 12 or 15 carbon atoms, an optionally substituted carbocyclic aryl such as optionally substituted phenyl, naphthyl or anthracenyl, or an optionally substituted heteroaromatic.

Particularly preferred R groups will contain a total of at least 4,5 or 6 carbon or hetero (N, O and/or S) atoms. For example, particularly preferred R groups include those comprising an optionally substituted carbon alicyclic group, such as an optionally substituted cyclohexyl group.

It is also generally preferred that the crosslinking agent of formula (I) contain at least two R groups which are the same or different non-hydrogen substituents. Preference is likewise given to crosslinkers of the formula (I) which contain three or four R groups which are identical or different non-hydrogen substituents.

Preferably, if the crosslinker of formula (I) contains a single R group, then the coating composition containing such crosslinker will also preferably contain an acid or acid source, such as a thermal acid generator compound, to facilitate the reaction of the coating composition.

As referred to herein, suitable heteroalkyl groups include optionally substituted C1-20 alkoxy, preferably optionally substituted alkylthio having from 1 to about 20 carbon atoms; optionally substituted alkylsulfinyl preferably having from 1 to about 20 carbon atoms; optionally substituted alkylsulfonyl groups preferably having from 1 to about 20 carbon atoms; and optionally substituted alkylamines preferably having 1 to about 20 carbon atoms.

As referred to herein, the term "carboalicyclic group" means that each ring member of the non-aromatic group is carbon. A carbon alicyclic group may have one or more internal ring carbon-carbon double bonds, with the proviso that the ring is not an aromatic ring. The term optionally substituted "cycloalkyl" means that each ring member of the nonaromatic group is carbon and the carbocyclic ring does not have any internal ring carbon-carbon double bonds. For example, cyclohexyl, cyclopentyl, and adamantyl are cycloalkyl groups as well as carbon alicyclic groups. Carboalicyclic and cycloalkyl groups can comprise one ring or a plurality (e.g., 2,3, 4, or more) of bridged, fused, or otherwise covalently linked rings.

As referred to herein, "heteroaryl" includes aromatic 5-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic ring systems having 1-3 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic), selected from O, N or S (e.g., carbon atoms and 1-3, 1-6, or 1-9 heteroatoms N, O or S, respectively if monocyclic, bicyclic, or tricyclic), wherein 0, 1,2,3, or 4 atoms of each ring may be substituted with a substituent. Examples of heteroaryl groups include pyridyl, furyl (furyl/furyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, and the like.

"optionally substituted"various materials and substituents (including groups A, B, X and Y of formula (I) above) may be suitably substituted at one or more available positions, for example by: halogen (F, Cl, Br, I); a nitro group; a hydroxyl group; an amino group; alkyl radicals, e.g. C _1-8 An alkyl group; alkenyl radicals, e.g. C _2-8 An alkenyl group; alkylamino radicals, e.g. C _1-8 An alkylamino group; carbocyclic aryl groups such as phenyl, naphthyl, anthracenyl, and the like; and so on.

In a generally preferred aspect, the resin and crosslinker components of the coating composition prior to heat treatment are distinct and separate materials, i.e., the resin component and crosslinker component are not covalently linked. In certain other embodiments, the crosslinker component may be attached to the resin component, for example, covalently tethered in a pendant form.

A variety of resins can serve as the resin component of the primer coating composition.

Particularly preferred resins of the coating composition of the present invention may comprise polyester linkages. Polyester resins can be readily prepared by the reaction of one or more polyol reagents with one or more carboxyl group-containing (e.g., carboxylic acid, ester, anhydride, etc.) compounds. Suitable polyol agents include diols, glycerol and triols, such as diols, e.g., diols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, butanediol, pentanediol, cyclobutyl diol, cyclopentyl diol, cyclohexyl diol, dimethylolcyclohexane, and triols, e.g., glycerol, trimethylolethane, trimethylolpropane, and the like.

Preferred polyester resins for use in the antireflective compositions of the invention are disclosed in U.S.8,501,383; u.s.2011/0033801; and U.S.7,163,751. As disclosed in those patent documents, the resin containing ester repeating units (polyester) can be suitably provided by polymerization of a carboxyl-containing compound (e.g., carboxylic acid, ester, anhydride, etc.) with a hydroxyl-containing compound, preferably a compound having a plurality of hydroxyl groups, such as a diol, e.g., ethylene glycol or propylene glycol, or glycerol, or other diols, triols, tetraols, and the like. In certain aspects, it is preferred that the ester functional groups are present as components of or within the polymer backbone, rather than as pendant or side chain units. The ester moieties may also be present as pendant groups, but preferably the polymer also contains ester functional groups along the polymer backbone. It is also preferred that the ester repeat units comprise aromatic substitution, such as optionally substituted carbocyclic aryl groups, for example optionally substituted phenyl, naphthyl or anthracenyl groups, in the form of side chains or more preferably along the polymer backbone.

The resin of the coating composition of the present invention may contain a variety of additional groups, such as cyanurate groups, as disclosed in U.S. patent nos. 6852421 and 8501383.

Particularly preferred matrix resins of the coating composition of the present invention may comprise one or more cyanurate and polyester linkages.

As discussed, for antireflective applications, suitably, one or more of the compounds reacted to form the resin include a moiety that can act as a chromophore to absorb radiation used to expose the overcoated photoresist coating. For example, phthalate compounds, such as phthalic acid or dialkyl phthalates (i.e., diesters, such as having 1-6 carbon atoms per ester, preferably dimethyl phthalate or diethyl phthalate) may be polymerized with aromatic or non-aromatic polyols and optionally other reactive compounds to give polyesters that are particularly useful in coating compositions for photoresists imaged at wavelengths below 200nm, such as 193 nm. The isocyanurate compound can also be polymerized with one or more polyols to provide resins suitable for use in the primer composition of the present invention. Resins for use in compositions having overcoated photoresists imaged at wavelengths below 300nm or below 200nm, such as 248nm or 193nm, naphthyl compounds may be polymerised, e.g. naphthyl compounds containing one or two or more carboxyl substituents, e.g. dialkyl naphthalates, especially di-C-naphthalates _1-6 An alkyl ester. Reactive anthracene compounds are also preferred, for example anthracene compounds having one or more carboxyl or ester groups, such as one or more methyl or ethyl ester groups.

The compounds containing chromophore units may also contain one or preferably two or more hydroxyl groups and are reacted with the carboxyl-containing compounds. For example, a phenyl compound or an anthracene compound having one, two, or more hydroxyl groups may be reacted with a carboxyl-containing compound.

In addition, the underlayer coating composition for antireflective purposes may contain a material containing chromophore units separated from a resin component that provides modulation of water contact angle (e.g., a resin containing photoacid-labile groups and/or base-reactive groups). For example, the coating composition can include polymeric or non-polymeric compounds containing units of phenyl, anthracene, naphthyl, and the like. However, it is generally preferred that the resin or resins that provide water contact angle modulation also contain chromophore moieties.

Preferably, the resin of the primer composition of the present invention will have a weight average molecular weight (Mw) of from about 1,000 to about 10,000,000 daltons, more typically from about 2,000 to about 100,000 daltons and a number average molecular weight (Mn) of from about 500 to about 1,000,000 daltons. The molecular weight (Mw or Mn) of the resin of the composition of the invention is suitably determined by gel permeation chromatography.

The resin component will be the major solid component of the primer coating composition in many preferred embodiments. For example, the resin suitably may be present in an amount of from 50 to 99.9% by weight of the total solids content of the coating composition, more typically from 80 to 95% by weight of the total solids content of the coating composition. As referred to herein, solids of a coating composition refers to all materials of the coating composition except for the solvent carrier.

In certain embodiments, the coating compositions of the present invention may comprise a crosslinker in addition to the crosslinker of formula (I). For example, the coating composition may include an amine-based crosslinker, such as a melamine material, including melamine resins, such as are manufactured by Cytec Industries and sold under the tradenames Cymel 300, 301, 303, 350, 370, 380, 1116 and 1130; glycolurils, including those available from Cytec Industries; and benzomelamine and urea based materials including resins such as benzomelamine resins available from Cytec Industries under the names Cymel 1123 and 1125, and urea resins available from Cytec Industries under the names Powderlink 1174 and 1196. Such amine-based resins can be prepared, for example, by reaction of acrylamide or methacrylamide copolymers with formaldehyde in alcoholic solution, or by copolymerization of N-alkoxy methacrylamides or methacrylamides with other suitable monomers, in addition to being commercially available.

The crosslinker component of the coating composition of the present invention is generally present in an amount between about 5 and 50 weight percent of the total solids of the coating composition (all components except the solvent carrier), more typically in an amount of about 5 to 25 weight percent total solids.

Particularly preferred coating compositions of the present invention may also contain a thermal acid generator compound. Thermally induced crosslinking of the coating composition by activation of the thermal acid generator is generally preferred.

Suitable thermal acid generator compounds for use in the coating composition include ionic or substantially neutral thermal acid generators, such as ammonium salts of arenesulfonic acids (e.g., ammonium tosylates), for catalyzing or promoting crosslinking during curing of the antireflective composition coating. Typically, the one or more thermal acid generators are present in the coating composition at a concentration of about 0.1 to 10 weight percent of the total dry components of the composition (all components except the solvent carrier), more preferably about 0.5 to 2 weight percent of the total dry components.

The coating compositions of the present invention, particularly for reflection control applications, may also contain additional dye compounds that absorb radiation used to expose an overcoated photoresist layer. Other optional additives include surface leveling agents such as those available under the trade name Silwet 7604, or surfactants FC 171 or FC 431 available from 3M Company.

The underlayer coating compositions of the present invention may also contain other materials, such as photoacid generators, including those discussed for use with an overcoated photoresist composition. For a discussion of such use of photoacid generators in antireflective compositions, see U.S. patent 6261743.

To make the liquid coating composition of the invention, the components of the coating composition are dissolved in a suitable solvent, such as one or more oxyisobutyrates, especially methyl 2-hydroxyisobutyrate, ethyl lactate, or one or more of the glycol ethers such as 2-methoxyethyl ether (diethylene glycol dimethyl ether), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; solvents having both ether and hydroxyl moieties, such as methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; 2-hydroxyisobutyric acid methyl ester; esters such as cellosolve methyl acetate, cellosolve ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and other solvents such as dibasic esters, propylene carbonate, and γ -butyrolactone. The concentration of the dry component in the solvent will depend on several factors, such as the coating method. Generally, the solids content of the primer coating composition ranges from about 0.5 to 20 weight percent of the total weight of the coating composition, preferably the solids content ranges from about 0.5 to 10 weight percent of the coating composition.

Exemplary Photoresist System

Photoresists for use with an underlayer coating composition typically comprise a polymer and one or more acid generators. It is generally preferred that the positive resist and resist polymer have functional groups that impart basic water solubility to the resist composition. For example, polymers comprising polar functional groups (such as hydroxyl or carboxylate groups) or acid labile groups that can release such polar moieties after photolithographic processing are preferred. Preferably, the polymer is used in the resist composition in an amount sufficient to render the resist developable with an aqueous alkaline solution.

The acid generator is also suitably used with polymers comprising repeating units containing aromatic groups such as optionally substituted phenyl including phenol, optionally substituted naphthyl, and optionally substituted anthracene. Polymers containing optionally substituted phenyl groups (including phenols) are particularly suitable for many resist systems, including those imaged with EUV and electron beam radiation. For positive-working resists, the polymer preferably also contains one or more repeat units that contain acid labile groups. For example, in the case of polymers containing optionally substituted phenyl or other aromatic groups, the polymer may comprise repeat units containing one or more acid labile moieties, such as polymers formed by polymerizing monomers of an acrylate or methacrylate compound with an acid labile ester (e.g., t-butyl acrylate or t-butyl methacrylate). Such monomers may be copolymerized with one or more other monomers (e.g., styrene or vinylphenol monomers) that include aromatic groups (e.g., optionally phenyl groups).

Preferred monomers for forming such polymers include: an acid-labile monomer having the following formula (V), a lactone-containing monomer of the following formula (VI), an alkali-soluble monomer of the following formula (VII) for adjusting a dissolution rate in an alkaline developer, and an acid-generating monomer of the following formula (VIII), or a combination comprising at least one of the foregoing monomers:

wherein each R is ^a Independently H, F, -CN, C _1-10 Alkyl or C _1-10 A fluoroalkyl group. In the acid deprotectable monomer of formula (V), R ^b Independently is C _1-20 Alkyl radical, C _3-20 Cycloalkyl radical, C _6-20 Aryl or C _7-20 Aralkyl, and each R ^b Is independently or at least one R ^b Bonded to adjacent R ^b To form a ring structure. In the lactone-containing monomers of formula (VI), L is a monocyclic, polycyclic or fused polycyclic C _4-20 Containing a lactone group. In the alkali-soluble monomer of formula (VII), W is a halogenated or non-halogenated, aromatic or non-aromatic C _2-50 A hydroxyl-containing organic group having a pKa of less than or equal to 12. In the acid-generating monomers of formula (VIII), Q is ester-containing or non-ester-containing and is fluorinated or non-fluorinated, and is C _1-20 Alkyl radical, C _3-20 Cycloalkyl radical, C _6-20 Aryl or C _7-20 Aralkyl group; a is ester-or non-ester-containing and is fluorinated or non-fluorinated and is C _1-20 Alkyl radical, C _3-20 Cycloalkyl radical, C _6-20 Aryl or C _7-20 An aralkyl group; z ^- Is an anionic moiety comprising a carboxylate, sulfonate, sulfonamide or sulfonimide anion; and G ⁺ Is a sulfonium or iodonium cation.

Exemplary acid deprotectable monomers include (but are not limited to):

or comprises at least oneCombinations of the foregoing monomers wherein R ^a Is H, F, -CN, C _1-6 Alkyl or C _1-6 A fluoroalkyl group.

Suitable lactone monomers can be monomers of the following formula (IX):

wherein R is ^a Is H, F, -CN, C _1-6 Alkyl or C _1-6 Fluoroalkyl, R is C _1-10 Alkyl, cycloalkyl or heterocycloalkyl, and w is an integer from 0 to 5. In formula (IX), R is directly attached to the lactone ring or typically to the lactone ring and/or one or more R groups, and the ester moiety is attached directly or indirectly via R to the lactone ring.

Exemplary lactone-containing monomers include:

or combinations comprising at least one of the foregoing monomers, wherein R ^a Is H, F, -CN, C _1-10 Alkyl or C _1-10 A fluoroalkyl group.

Suitable alkali soluble monomers may be monomers of the following formula (X):

wherein each R is ^a Independently H, F, -CN, C _1-10 Alkyl or C _1-10 Fluoroalkyl, A is hydroxyl-or non-hydroxyl-containing, ester-or non-ester-containing, fluorinated or non-fluorinated C _1-20 Alkylene radical, C _3-20 Cycloalkylene radical, C _6-20 Arylene radicals or C _7-20 Aralkylene, and x is an integer of 0 to 4, wherein when x is 0, A is a hydroxyl-containing C _6-20 An arylene group.

Exemplary alkali soluble monomers include those having the structure:

or combinations comprising at least one of the foregoing monomers, wherein R ^a Is H, F, -CN, C _1-6 Alkyl or C _1-6 A fluoroalkyl group.

Preferred acid generating monomers include those of formula (XI) or (XII):

wherein each R is ^a Independently H, F, -CN, C _1-6 Alkyl or C _1-6 Fluoroalkyl, A is fluorine-substituted C _1-30 Alkylene, fluorine substituted C _3-30 Cycloalkylene, fluorine substituted C _6-30 Arylene or fluorine substituted C _7-30 Alkylene arylene, and G ⁺ Is a sulfonium or iodonium cation.

Preferably, in formula (XI) and formula (XII), A is- [ (C (R) ¹ ) ₂ ) _x C(＝O)O] _b -C((R ² ) ₂ ) _y (CF ₂ ) _z A radical or ortho-, meta-or para-substituted-C ₆ F ₄ A group in which each R is ¹ And R ² Each independently is H, F, -CN, C _1-6 Alkyl or C _1-6 Fluoroalkyl, b is 0 or 1, x is an integer from 1 to 10, y and z are independently integers from 0 to 10, and the sum of y + z is at least 1.

Exemplary preferred acid generating monomers include:

or combinations comprising at least one of the foregoing monomers, wherein each R ^a Independently H, F, -CN, C _1-6 Alkyl or C _1-6 Fluoroalkyl, k is suitably an integer from 0 to 5; and G ⁺ Is a sulfonium or iodonium cation. G as mentioned in the various formulae herein ⁺ May be an acid generator as disclosed herein and comprises an oxo-dioxolane moiety and/or an oxo-dioxane moiety.

Preferred acid-generating monomers can include sulfonium or iodonium cations. Preferably, in formula (IV), G ⁺ Having formula (XIII):

wherein X is S or I; each R ⁰ Is halogenated or non-halogenated and is independently C _1-30 Alkyl, polycyclic or monocyclic C _3-30 Cycloalkyl, polycyclic or monocyclic C _4-30 Aryl or a combination comprising at least one of the foregoing groups, wherein R is when X is S ⁰ One of the groups is optionally linked to an adjacent R by a single bond ⁰ And a is 2 or 3, wherein a is 2 when X is I, or 3 when X is S.

Exemplary acid generating monomers include those having the formula:

polymers having acid labile deblocking groups particularly suitable for use in positive-acting chemically amplified photoresists of the invention have been disclosed in european patent application 0829766a2 (polymers with acetals and ketal polymers) and european patent application EP0783136a2 (including 1) styrene; 2) hydroxystyrene; and 3) acid labile groups, specifically alkyl acrylate acid labile groups) units.

Other preferred resins for photoresists imaged below 200nm, such as 193nm, comprise units of the following general formulae (I), (II) and (III):

preferred resins for photoresists imaged at below 200nm, such as 193nm, comprise units of the following general formulae (I), (II) and (III):

wherein: r ₁ Is (C) ₁ -C ₃ ) An alkyl group; r is ₂ Is (C) ₁ -C ₃ ) An alkylene group; l is ₁ Is a lactone group; and n is 1 or 2.

The molecular weight and polydispersity of the polymers used in the photoresists of the invention may suitably vary widely. Suitable polymers include M _w Those polymers that are from about 1,000 to about 50,000, more typically from about 2,000 to about 30,000 and have a molecular weight distribution of about 3 or less, more typically a molecular weight distribution of about 2 or less.

Preferred negative-acting compositions of the present invention comprise a mixture of a material that will cure, crosslink or harden upon exposure to acid and two or more acid generators as disclosed herein. Preferred negative-acting compositions comprise a polymeric binder (e.g., a phenolic or non-aromatic polymer), a crosslinker component, and a photoactive component of the present invention. Such compositions and their use are disclosed in european patent application 0164248 and U.S. patent No. 5,128,232 (Thackeray et al). Preferred phenolic polymers for use as the polymeric binder component include novolacs and poly (vinylphenol), such as those described above. Preferred crosslinkers include amine-based materials (including melamine), glycolurils, benzoguanamine-based materials, and urea-based materials. Melamine-formaldehyde polymers are generally particularly suitable. Such crosslinkers are commercially available, for example melamine polymers, glycoluril polymers, urea-based polymers and benzoguanamine polymers, such as those sold by Cytec under the trade names Cymel 301, 303, 1170, 1171, 1172, 1123 and 1125 and beette 60, 65 and 80.

Particularly preferred photoresists of the invention can be used in immersion lithography applications. For a discussion of preferred immersion lithography photoresists and processes, see, e.g., U.S.7968268 to Rohm and Haas Electronic Materials.

Photoresists of the invention may also contain a single acid generator or a mixture of distinct acid generators, typically a mixture of 2 or 3 different acid generators, more typically a mixture consisting of a total of 2 distinct acid generators. The photoresist composition comprises an acid generator employed in an amount sufficient to produce a latent image in a coating layer of the composition upon exposure to activating radiation. For example, the acid generator will suitably be present in an amount of from 1 to 20 wt.%, based on the total solids of the photoresist composition.

Suitable acid generators are known in the art of chemically amplified photoresists and include, for example: onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives such as 2-nitrobenzyl-p-toluenesulfonate, 2, 6-dinitrobenzyl-p-toluenesulfonate and 2, 4-dinitrobenzyl-p-toluenesulfonate; sulfonates such as 1,2, 3-tris (methanesulfonyloxy) benzene, 1,2, 3-tris (trifluoromethanesulfonyloxy) benzene, and 1,2, 3-tris (p-toluenesulfonyloxy) benzene; diazomethane derivatives such as bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane; glyoxime derivatives such as bis-O- (p-toluenesulfonyl) - α -dimethylglyoxime and bis-O- (n-butanesulfonyl) - α -dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds such as 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine.

As mentioned herein, the acid generator may generate an acid upon exposure to activating radiation, such as EUV radiation, electron beam radiation, 193nm wavelength radiation, or other radiation sources. The acid generator compounds as referred to herein may also be referred to as photoacid generator compounds.

The photoresist of the present invention may also contain other materials. Other optional additives include, for example, actinic and contrast dyes, anti-striation agents, plasticizers, speed enhancers and sensitizers. Such optional additives will typically be present in the photoresist composition at relatively small concentrations.

Alternatively or additionally, other additives may include quenchers that are non-photodestructible bases, such as those based on hydroxides, carboxylates, amines, imines, and amides. Preferably, such quenchers comprise C _1-30 Organic amines, imines or amides, or C which may be a strong base (e.g. hydroxide or alkoxide) or a weak base (e.g. carboxylate) _1-30 Quaternary ammonium salts. Exemplary quenchers include amines, such as tripropylamine, dodecylamine, tris (2-hydroxypropyl) amine, tetrakis (2-hydroxypropyl) ethylenediamine; arylamines such as diphenylamine, triphenylamine, aminophenol and 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, hindered amines such as Diazabicycloundecene (DBU) or Diazabicyclononene (DBN), or ion quenchers including quaternary alkylammonium salts such as tetrabutylammonium hydroxide (TBAH) or tetrabutylammonium lactate.

Surfactants include fluorinated and non-fluorinated surfactants and are preferably non-ionic. Exemplary fluorinated nonionic surfactants include perfluoro C ₄ Surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluoro-diols such as POLYFOX PF-636, PF-6320, PF-656 and PF-6520 fluorosurfactants from Omnova.

The photoresist further comprises a solvent generally suitable for dissolving, dispensing and coating the components used in the photoresist. Exemplary solvents include anisole; alcohols including ethyl lactate, 1-methoxy-2-propanol and 1-ethoxy-2-propanol; esters, including n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate; ketones, including cyclohexanone and 2-heptanone; and combinations comprising at least one of the foregoing solvents.

Lithographic processing

In use, the coating composition of the present invention is applied as a coating to a substrate by any of a variety of methods, such as spin coating. The coating composition is typically applied to the substrate at a dry layer thickness of between about 0.02 and 0.5 μm, preferably between about 0.04 and 0.20 μm. The substrate is suitably any substrate used in a process involving a photoresist. For example, the substrate may be a silicon, silicon dioxide, or aluminum-aluminum oxide microelectronic wafer. Gallium arsenide, silicon carbide, ceramic, quartz, or copper substrates may also be used. Substrates for liquid crystal display or other flat panel display applications, such as glass substrates, indium tin oxide coated substrates, and the like, are also suitably employed. Substrates for optical and optoelectronic devices (e.g., waveguides) may also be employed.

Preferably, the applied coating is cured before the photoresist composition is applied over the primer composition. The curing conditions will vary with the components of the primer composition. Specifically, the curing temperature will depend on the particular acid or acid (heat) generator employed in the coating composition. Typical curing conditions are about 80 ℃ to 225 ℃ for about 0.5 to 5 minutes. The curing conditions are preferably such that the coating composition coating is substantially insoluble in the photoresist solvent and developer solution used.

After such curing, a photoresist is applied to the surface of the applied coating composition. As with the application of the layer of the primer composition, the overcoated photoresist can be applied by any standard method, such as by spin coating, dip coating, meniscus coating, or roll coating. After coating, the photoresist coating is typically dried by heating to remove the solvent, preferably until the resist layer is tack free. Optimally, substantially no intermixing of the bottom composition layer with the overcoated photoresist layer should occur.

The resist layer is then imaged with activating radiation, such as 248nm, 193nm or EUV radiation through a mask in a conventional manner. The exposure energy is sufficient to effectively activate the photosensitive components of the resist system to produce a patterned image in the resist coating. Typically, the exposure energy ranges from about 3 to 300mJ/cm ² And in part, on the exposure tool and the particular resist and resist process employed. Exposed resistThe agent layer may be subjected to a post-exposure bake as necessary to create or enhance a solubility differential between the exposed and unexposed areas of the coating. For example, negative acid-hardening photoresists typically require post-exposure heating to induce acid-promoted crosslinking reactions, and many chemically amplified positive-acting resists require post-exposure heating to induce acid-promoted deprotection reactions. Typically, the post-exposure bake conditions include a temperature of about 50 ℃ or greater, more specifically a temperature in the range of about 50 ℃ to about 160 ℃.

The photoresist layer may also be exposed to an immersion lithography system, i.e., where the space between the exposure tool (especially the projection lens) and the photoresist-coated substrate is occupied by an immersion fluid, such as water or water mixed with one or more additives, such as cesium sulfate, which provides a fluid of enhanced refractive index. Preferably, the immersion fluid (e.g. water) has been treated to avoid bubbles, e.g. the water may be degassed to avoid nanobubbles.

Reference herein to "immersion exposure" or other similar terms indicates that exposure is conducted with such a fluid layer (e.g., water or water with additives) interposed between the exposure tool and the coated photoresist composition layer.

The exposed photoresist layer is then treated with a suitable developer capable of selectively removing portions of the film to form a photoresist pattern. In a negative tone development process, the unexposed regions of the photoresist layer can be selectively removed by treatment with a suitable non-polar solvent. See u.s.2011/0294069 for a suitable procedure for negative tone development. Typical non-polar solvents for negative tone development are organic developers such as solvents selected from ketones, esters, hydrocarbons and mixtures thereof, for example acetone, 2-hexanone, 2-heptanone, methyl acetate, butyl acetate and tetrahydrofuran. The photoresist material used in the NTD process preferably forms a photoresist layer that can form a negative image with an organic solvent developer or a positive image with an aqueous base developer such as a tetraalkylammonium hydroxide solution. Preferably, NTD photoresists are based on polymers with acid sensitive (deprotectable) groups that form carboxylic acid and/or hydroxyl groups upon deprotection.

Alternatively, development of the exposed photoresist layer can be accomplished by treating the exposed layer with a suitable developer that can selectively remove either the exposed portions of the film (where the photoresist is positive-type) or the unexposed portions of the film (where the photoresist is cross-linkable in the exposed areas, i.e., negative-type). Preferably, the photoresist is positive working, based on a polymer having acid sensitive (deprotectable) groups that form carboxylic acid groups upon deprotection, and the developer is preferably a metal ion free tetraalkylammonium hydroxide solution, such as 0.26N aqueous tetramethylammonium hydroxide. The pattern is formed by development.

The developed substrate can then be selectively processed according to procedures well known in the art on those substrate areas that are devoid of photoresist, such as chemically etched or plated areas that are devoid of photoresist. Suitable etchants include hydrofluoric acid etching solutions and plasma gas etchants, such as oxygen plasma etchants. The plasma gas etch removes the bottom coating.

The following non-limiting examples illustrate the invention.

Example 1: preparation of tetrakis (cyclohexyloxymethyl) -3 a-butyl-6 a-methylglycinamide

The title compound, tetrakis (cyclohexyloxymethyl) -3 a-butyl-6 a-methylglycinamide, was prepared as shown in the immediately preceding scheme and as follows:

(a) to a 100mL round bottom flask equipped with a magnetic stir bar was dissolved water (57mL) containing 2, 3-heptanedione (3.915g, 30.5 mmol). Phosphoric anhydride (4.86g, 17.1mmol) was fed to this solution and the solution was allowed to stir for 10 minutes. To this resulting clear, colorless solution was fed urea (5.393g, 89.8mmol) and the entire reaction mixture was stirred at ambient temperature for 20 minutes. The resulting heterogeneous solution was cooled to ambient temperature and the solid was collected by filtration. The solid was washed with cold water and then dried under high vacuum to give 3 a-butyl-6 a-methyl-glycoluril as a white powder, 2.74g (42% yield). ¹ H NMR(d ₆ -DMSO)δ＝7.14(2H,s),7.06(2H,s),1.59(2H,m),1.35(7H,m),0.87(3H,t,J＝7.5Hz)ppm。 ¹³ C NMR(d ₆ -DMSO)δ＝160.22,160.12,77.83,76.02,35.48,25.19,22.95,21.97,14.34ppm。

(b) A25 mL scintillation vial equipped with a magnetic stir bar was charged with 3 a-butyl-6 a-methyl-glycoluril (1.71g, 8.1mmol) and 8mL water. To this mixture was fed trioxymethylene (1.91g, 63.7mmol) and 1mL of 5% NaOH (16%). The mixture was heated to 50 ℃ and allowed to stir overnight. The clear, homogeneous solution was filtered while stirring hot and the resulting solution was evaporated to dryness to give a viscous oil, which was used in the next step without any further purification.

(c) A100 mL round bottom flask equipped with a magnetic stir bar was fed with the aforementioned viscous oil, cyclohexanol (20g, 199.7mmol), and concentrated nitric acid (4.2mL, 65.4 mmol). This mixture was heated to 60 ℃ while stirring and kept at that temperature overnight. The resulting mixture was then neutralized with 5% sodium hydroxide (solution) and subsequently extracted with dichloromethane (2 ×). The combined organic fractions were washed with brine, dried over anhydrous magnesium sulfate and concentrated by rotary evaporation to give a crude product mixture which after standing overnight at 2 ℃ gave tetrakis (cyclohexyloxymethyl) -3 a-butyl-6 a-methyl glycoluril (0.38g, 7.1% in two steps) as colorless needles which were collected by vacuum filtration. Additional product was collected by second crystallization to give the title compound tetrakis (cyclohexyloxymethyl) -3 a-butyl-6 a-methylglycine in a total yield of up to 1.1 g (20.7% over two steps). ¹ H NMR(d ₆ -DMSO)δ＝5.22(1H,d,J＝10Hz),5.20(1H,d,J＝10Hz),5.01(1H,d,J＝10Hz),4.95(1H,d,J＝10Hz),3.38(4H,m)2.28(2H,dd,J＝7.5,7.5Hz),1.84(3H,s),1.73(6H,m),1.64(6H,m),1.46(4H,m),1.39(4H,m),1.22-1.11(20H,m),0.91(3H,dd,J＝5.0,5.0Hz)ppm。13C NMR(d6-DMSO)158.04,75.79,74.04,70.82,70.57,68.68,39.72,35.83,28.65,26.37,25.82,24.26,22.53,17.10,14.28ppm。ESI-MS m/z＝683[M+Na] ⁺ 。

Example 2: condensation of tetra (hydroxymethyl) glycoluril with cyclohexanol

Concentrated nitric acid (4.4 equiv.) was added to tetrakis (hydroxymethyl) glycoluril (1.0 equiv.) suspended in cyclohexanol (20.0 equiv.). This mixture was heated to dissolve the glycoluril, followed by stirring at high temperature until the reaction was complete. The final reaction mixture was cooled to ambient temperature, neutralized with dilute caustic, dried over magnesium sulfate, and concentrated by rotary evaporation. The final product was isolated by crystallization from the crude reaction mixture or by purification via column chromatography (EtOAc: Hex) to give the target compound as a white crystalline solid.

Example 3: coupling chloromethyl cyclohexyl ether with glycoluril

To glycoluril (1.0 eq) dissolved in tetrahydrofuran were added chlorocyclohexyl ether (4.4 eq) and dilute sodium hydroxide (8.8 eq). The solution was stirred at high temperature until completion. The resulting solution was extracted with dichloromethane, dried over magnesium sulfate, and concentrated by rotary evaporation. The final product was isolated by crystallization or column chromatography (EtOAc: Hex) to afford the title compound as a white crystalline solid.

Example 4: coupling of cyclohexanol with tetra (chloromethyl) glycoluril

Tetrakis (chloromethyl) glycoluril (1.0 eq) dissolved in tetrahydrofuran was slowly added to a solution of cyclohexanol (4.4 eq) and sodium hydride (8.8 eq) in tetrahydrofuran, maintained at 0C. The resulting reaction mixture was heated to 60C and allowed to stir overnight. The resulting solution was cooled to 0C and quenched by careful addition of water. The resulting mixture was extracted with dichloromethane, dried over magnesium sulfate, and concentrated by rotary evaporation. The final product was isolated by crystallization or column chromatography (EtOAc: Hex) to afford the title compound as a white crystalline solid.

Example 5: coupling of cyclohexanol with tetra (acetoxymethyl) glycoluril

Tetrakis (acetoxymethyl) glycoluril (1.0 equiv.) dissolved in tetrahydrofuran was slowly added to a solution of cyclohexanol (4.4 equiv.) and sodium hydride (8.8 equiv.) in tetrahydrofuran, maintained at 0 ℃. The resulting reaction mixture was heated to 60 ℃ and allowed to stir overnight. The resulting solution was cooled to 0 ℃ and quenched by careful addition of water. The resulting mixture was extracted with dichloromethane, dried over magnesium sulfate, and concentrated by rotary evaporation. The final product was isolated by crystallization or column chromatography (EtOAc: Hex) to afford the title compound as a white crystalline solid.

Example 6: synthesis of tetra (n-hexyl) glycoluril

Containing 1,3,4, 6-tetra (hydroxymethyl) tetrahydroimidazo [4,5-d]Imidazole-2, 5(1H,3H) -dione (1g, 3.8mmol) in 2ml DMSO was dissolved. Next, 0.15ml nitric acid (65%) and n-hexanol (9.5ml, 76.3mmol) were added to the solution and the mixture was heated at 60 ℃ for 16 hours. After the reaction was complete, the reaction liquid was cooled and 1N NaOH at about pH 7 was added. About 100ml of ethyl acetate were used to extract the mixture and the organic phase was washed 2 times with supersaturated NaCl (aqueous) solution. In the presence of Na ₂ SO ₄ After drying, the solvent is removed. The crude compound was purified by flash chromatography (heptane/EtOAc). A yield (%) of 0.15g of a colorless viscous oil product was obtained, ¹ H NMR(600MHz,DMSO-d6):δppm)5.50(s,2H),4.73(m,8H),3.36(m,8H),1.46(m,8H),1.24(m,26H),0.85(t,12H)。

example 7: synthesis of tetra (n-butyl) glycoluril

Containing 1,3,4, 6-tetra (hydroxymethyl) tetrahydroimidazo [4,5-d]Imidazole-2, 5(1H,3H) -dione (1.88g, 7.2mmol) in 1.5ml DMSO was dissolved. Next, 0.15ml of nitric acid (65%) and n-BuOH (13.12ml, 143mmol) were added to the solution and the mixture was heated at 60 ℃ for 16 hours. After the reaction was complete, the reaction liquid was cooled and 1N NaOH at about pH 7 was added. About 100ml of ethyl acetate were used for the extraction mixture and the organic phase was washed 2 times with supersaturated NaCl (aqueous) solution. In the presence of Na ₂ SO ₄ After drying, the solvent is removed. The crude compound was purified by flash chromatography (heptane/EtOAc). A yield (11%) of 0.38g of a colorless viscous oil product was obtained, ¹ H NMR(600MHz,DMSO-d6):δ(ppm)5.52(s,2H),4.73(m,8H),3.35(m,8H),1.46(m,8H),1.29(m,8H),0.85(t,12H)。

example 8: synthesis of Tetrakis (tetrahydro-4-pyranol) glycoluril

Containing 1,3,4, 6-tetra (hydroxymethyl) tetrahydroimidazo [4,5-d]Imidazole-2, 5(1H,3H) -dione (3g, 11.4mmol) in tetrahydro-4-pyranol (11ml, 114mmol) was dissolved. Then, 0.15ml nitric acid (65%) was added to the solution and the mixture was heated at 60 ℃ for 16 hours. After the reaction was complete, the reaction liquid was cooled and 1N NaOH at about pH 7 was added. About 100ml of ethyl acetate were used for the extraction mixture and the organic phase was washed 2 times with supersaturated NaCl (aqueous) solution. In the presence of Na ₂ SO ₄ After drying, the solvent is removed. The crude compound was purified by flash chromatography (MC/acetone). A colorless viscous oil product was obtained. ¹ H NMR(600MHz,DMSO-d6):δ(ppm)5.57(s,2H),4.84(m,8H),3.78(m,8H),3.57(m,4H),3.29(m,8H),1.82(m,8H),1.40(m,8H)。

Example 9: synthesis of tetrakis (4-ethylcyclohexanol) glycoluril

Containing 1,3,4, 6-tetra (hydroxymethyl) tetrahydroimidazo [4,5-d]Imidazole-2, 5(1H,3H) -dione (1.99g, 7.6mmol) in 1.5ml DMSO was dissolved. Subsequently, 0.3ml nitric acid (65%) and 4-ethylcyclohexanol (10.5ml, 75.9mmol) were added to the solution and the mixture was heated at 60 ℃ for 16 h. After the reaction was complete, the reaction liquid was cooled and 1N NaOH at about pH 7 was added. About 100ml of ethyl acetate were used for the extraction mixture and the organic phase was washed 2 times with supersaturated NaCl (aqueous) solution. In the presence of Na ₂ SO ₄ After drying, the solvent is removed.

Example 10: synthesis of tetrakis (4-methylcyclohexanol) glycoluril

Containing 1,3,4, 6-tetra (hydroxymethyl) tetrahydroimidazo [4,5-d]3ml of DMSO of imidazole-2, 5(1H,3H) -dione (1.25g, 4.8mmol)Dissolving. Then, 0.3ml nitric acid (65%) and 4-methylcyclohexanol (5.9ml, 47.7mmol) were added to the solution and the mixture was heated at 60C for 16 hours. After the reaction was complete, the reaction liquid was cooled and 1N NaOH at about pH 7 was added. About 100ml of ethyl acetate were used to extract the mixture and the organic phase was washed 2 times with supersaturated NaCl (aqueous) solution. In the presence of Na ₂ SO ₄ After drying, the solvent is removed.

Example 11: thermal degradation of crosslinkers by TGA

This example shows the increased thermal degradation characteristics (as corresponding to its thermogravimetric analysis (TGA) decomposition profile) of the inventive crosslinker molecules.

As referred to herein, the thermogravimetric analysis (TGA) decomposition temperature of the sample material (specifically the crosslinker compound) is determined by the following protocol. Thermogravimetric analysis (TGA) decomposition temperature was determined by measuring the change in mass of the test sample with a mass spectrometer while the temperature was increasing. As the temperature increases, the weight change of the sample is measured. The temperature at which 50% mass loss is recorded is determined as the decomposition temperature of the material. Commercially available (e.g., PerkinElmer) thermogravimetric analysis equipment can be used for the determination.

The TGA decomposition temperatures of the following crosslinkers shown in table 1 were measured. As shown in table 1, tetrakis (cyclohexyloxymethyl) glycoluril (TcyGU) has the highest decomposition temperature and is then the tetrakis (hexyloxy) - (TnhyGU), tetrakis (n-butoxymethyl) - (TnbGU), tetrakis (phenoxymethyl) - (TPhmGU), tetrakis (isopropoxymethyl) - (TisoproGU) and tetrakis (methoxymethyl) - (TMGU) derivatives, respectively. The structure of these crosslinker compounds is as follows:

	TMGU	TisoproGU	TPhmGU	TnbuGU	TnhGU	TcyGU
							temperature (. degree.C.)	231.08	213.85	224.74	257.08	304.44	332.84

TABLE 1

EXAMPLE 12 Peel/swell results for Slow Heat acid Generator formulations

This example shows the effectiveness of a heavy chain crosslinker (TcyGU) in forming BARC during thermal bake. The control compound tetrakis (methoxymethyl) glycoluril (TMGU) is known to vaporize during high heat baking temperatures (e.g. 205 ℃) and therefore gives high peel/swell values, which indicates that poor films with high solubility are produced under aqueous conditions in subsequent processing steps. The heavy chain crosslinker TcyGU of the present invention does not vaporize at these temperatures and is very reactive as a crosslinker, so the resulting BARC film does not dissolve under subsequent aqueous processing steps and gives low peel/swell values. As a comparison, the crosslinkers miggu and MP-TMGU were evaluated and did not act as effective crosslinkers under these process conditions and provided very poor peel/swell values.

Preparation of an antireflective composition

0.23g of TMGU (example F1 in table 2 below) or TcyGU (example F2 in table 2 below) or MiPGU (example F3 in table 2 below) or MP-TMGU (example F4 in table 2 below), 0.006g p-TSA benzylammonium salt, 0.001g of the fluorochemical surfactant Polyfox 656 from OMNOVA solutions inc, 0.53g of isocyanurate based polyester COP-BTTB (korean chemotherapeutics, Mw 3K, PDI 1.4) and 19.2g of methyl 2-Hydroxyisobutyrate (HBM) were mixed to obtain a 3.8 wt% solution based on the total weight of the composition. The solution was filtered through a PTFE microfilter having a pore size of 0.45 microns to obtain a BARC composition. A comparative formulation was prepared by mixing 0.23g of TMGU, 0.006g p-TSA ammonium salt, 0.001g of the fluorochemical surfactant Polyfox 656 from OMNOVA solutions inc, 0.53g of the isocyanurate based polyester resin COP-BTTB (korean chemitics, Mw 3K, PDI 1.4) and 19.2g of methyl 2-Hydroxyisobutyrate (HBM) (example C1).

Procedure for measuring solvent resistance (swelling/peeling)

Each sample solution tested for solvent resistance was spin coated onto a Si wafer and baked at 205C for 60 seconds. The film thickness on the Si wafer (THK of the coating columns of the table below) was measured using ellipsometry. The PGME/PGMEA 70:30 wt% mixed solution, typically used in the photoresist field, was then poured onto the surface of the BARC film and allowed to stand for 90 seconds. The wafer was then spun at 4000rpm for 60 seconds. The thickness was measured again (THK of the stripped column of the table below) and the final thickness was measured again after an additional 60 seconds of baking at 110C (THK of the baked column of the table below). The difference between the final bake and spin dry is reported as the swell value and the difference from the initial thickness is reported as the peel value.

TABLE 2

Example 13: sublimation results of BARC films containing various x-linkers

This example shows the exhibited outgassing thickness of the three best performing compounds from example 12 at a QCM bake temperature of 205 ℃. The control compound TMGU had a high outgassing thickness, which was responsible for the poor performance in example 12 above. The compound TcyGU of the invention gave a very low degassing thickness, which is responsible for the good performance in example 12. Best performance comparison compound MP-TMGU gave the working outgassing thickness values and contributed to the poor results in example 12 above.

Preparation of antireflective compositions for sublimation testing

0.23g of TMGU (example F5 in table 3 below) or TcyGU (example F6 in table 3 below) or MP-TMGU (example F7 in table 3 below), 0.001g of the fluorochemical surfactant Polyfox 656 from OMNOVA solutions inc, 0.53g of the isocyanurate based polyester COP-BTTB (korean chemotics, Mw ═ 3K, PDI ═ 1.4) and 19.2g of methyl 2-Hydroxyisobutyrate (HBM) were mixed to obtain a 3.8 wt% solution based on the total weight of the composition. The solution was filtered through a PTFE microfilter having a pore size of 0.45 microns to obtain a BARC composition without a thermal acid generator to avoid cross-linking effects on the sublimation results.

General procedure for measuring sublimation

A Quartz Crystal Microbalance (QCM) was used to determine sublimation content.

Each sample solution that was tested sublimed was spin coated onto a Si wafer and baked at 205C on a special hot plate that brought the wafer into almost direct contact with a quartz crystal sample holder. The b/a frequency was measured by a frequency counter and converted into a thickness determination of the sublimed material in the QCM plate.

TABLE 3

EXAMPLE 14 lithography

This example shows that the heavy chain crosslinker TcyGU of the present invention produces comparable results to the reference compound TMGU when the photoresist is placed on top of the resulting BARC material containing the crosslinker and processed at low temperature. This demonstrates the utility of heavy chain crosslinkers for these and other applications.

The BARC compositions of examples F1 and C1 were each spin coated at 1500rpm on a 150mm silicon wafer, followed by baking at 205 ℃ for 60 seconds using a TEL Mark 8 wafer coating track machine. BARC coating after bakingLayer thickness of

Dow (Dow) UV ^TM 1610DUV photoresist was spin-coated on top of the BARC coating and baked at 100 ℃ for 60 seconds, resulting in a 240nm thick photoresist layer. The photoresist was then exposed through a target mask at 0.65NA using a 248nm KrF wafer stepper. Next, the photoresist layer was subjected to a post exposure bake at 120 ℃ for 60 seconds, and then a Dow MF was used ^TM The CD-26TMAH developer was developed in a standard 60 second single puddle process. Inspection of the critical dimension of the pattern was performed by scanning electron microscopy to check the pattern collapse tolerance of the photoresist on each BARC.

Claims

1. A method of forming a photoresist relief image, comprising:

a) coating a substrate with a layer of a coating composition comprising:

1) a resin comprising one or more cyanurate groups and a polyester bond; and

2) a crosslinking agent comprising the structure of formula (I):

wherein in formula (I):

each R is independently selected from substituted alkyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, or optionally substituted heterocycloalkyl,

wherein at least one R group comprises at least 5 carbon or heteroatoms;

r' and R "are each independently selected from hydrogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted carbocyclic aryl, or optionally substituted heteroaryl; and

b) coating a photoresist composition layer on the coating composition layer.

2. The method of claim 1, wherein the crosslinker component has a molecular weight of at least 400 daltons.

3. The method of claim 1 or 2, wherein the crosslinker component has a molecular weight of less than 1500 daltons.

4. The method of any one of claims 1-3, wherein the crosslinker component has a degradation temperature greater than 250 ℃.

5. The method of any one of claims 1-4, wherein one or more R groups comprise an optionally substituted carbon cycloaliphatic moiety.

6. The process of any one of claims 1 to 5, wherein the photoresist composition is imaged with activating radiation and the imaged photoresist composition layer is developed resulting in a photoresist relief image.

7. The method of any one of claims 1-6, wherein the coating composition layer is heat treated prior to applying the photoresist composition layer.

8. The method of any one of claims 1 to 7, wherein the crosslinking agent comprises a structure represented by one of the following formulae:

9. a coated substrate comprising:

a substrate having thereon:

a) a coating composition comprising:

1) a resin comprising one or more cyanurate groups and a polyester bond; and

2) a crosslinker component;

b) a photoresist composition layer on the coating composition layer,

wherein the crosslinker component prior to reaction with the resin comprises the structure of formula (I):

wherein in formula (I):

wherein at least one R group includes at least 5 carbon or heteroatoms;

r' and R "are each independently selected from hydrogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted carbocyclic aryl, or optionally substituted heteroaryl.

10. A crosslinking agent comprising the structure of formula (I):

wherein in formula (I):

wherein at least one R group includes at least 5 carbon atoms or heteroatoms;